Note: Descriptions are shown in the official language in which they were submitted.
~166631
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BIS ARYL-~ZO DERIV~TIVES OF
2,3-NAPHTHALENEDIOL ~ND ELECTROPHOTOGRAPHIC
LIQUID DEVELOPER COMPOSITIONS CONTU NING THEM
Thi- lnventlon r-late- to nov-l cbemlcal
compound~ and to liquit electtophotogr-phic dev-l-
oper compo~itlon~ containing ~uch compound~ as
colorant~
Electrophotographic developer~ r- used for
teveloping electrostatic charge pattern~ or, in other
words, for making l~tent electrostat~c image6
vi~ible For instance, in th- electrophotographic
copying of document~ an electrostatic charge pattern
i~ formcd on J photoconductivc ~urface and tben i~
made vi~ibl- with a develop-r compo-ition or the
ch-rge p~ttern i~ tran~f-rred to a sheet of paper or
oth-r ~urfac- where it l- then developed and made
vi~ibl-
Both dry and liquid developer compo~itions
r- known Liquid d-v-lop-r- have cert-in ~tvan-
tJg~ uch J~ ~mall particle ~ize, which permlts
th-ir u~- ln sy~tem~ requiring fln- lin~ resolu-
tion. Llquid d-v-lop-r~ norm-lly r- compo~ed of -
fin-ly divid-d pigment di~p-r~ed in an insulating
2S c-rri-r liquid ~uch - vol-tll- hydrocarbon
mlxtur- To blnd th- pigment to an imaging surf-ce a
bind-r r-~ln c-n l-o b- lncluded ln th- di~per-
~lon. Oth-r po~lbl- compon-nt~ include charge
control g-nt~ whlch ~t-blllze th- collold-l di~per-
~lon by r-t~rdlng the ~ettllng of the plgment from
th- c-r~l-r llquld.
Of th- m~ny color-d ~ub~t-nce~ that h-v-
b--n ur-d ~ plgment~ for llquld d-veloper-, c-rbon
bl-c~ h-~ b-en ~pecl-lly popular. Varlou~ bl-c~ and
color-d orgJnic compound~ h-v~ o becn u~ed
,' ~.
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Thc p-tcnt to Ford t Jl U.S. 4,14S,299
dl~clo~c~ ~ cl-~r of organlc compound~ thJt ~r-
u-eful ~ plgment~ ln llquld l-ctrophotogr-phic
d~v~lop~r~ Th~ compound~ ~rc bl~ ryl--zo
d~rlvatl~ of 2,3-naphth~len~dlol When disper~d,
thelr opeic-l d~n~lty 1- ~ub~t~nt~lly n-utr-l; th~t
1~, thcy rc bl-c~ or nc~rly blac~ in huc Th~y
~l~o form rea~on-bly ~tablc dl~per~lon~ ln hydro-
c~rbon c~rrler llquld~ ruch ~ the commonly u--d
l~op~r~fflnlc llqu$d c-rrl-r-. Ll~ m~ny organlc
dycr, ho~cver, member~ of thl- cl-~ h~vc poorer
light ~t-blllty th-n would bc de~lr-d. Con---
qu-ntly, th- lmage~ devclopet wlth them tend to f~dc
whcn cxpo~cd to llght or ultr~vlol-t r-dl-tion ov~r
cxtcndcd pcrlod~ of tlm .
~ -n--d thcr for- cxlrt~ for pigmcnt~ h-vlng
ncutr-l dcn~lty nd goot dl~pcr~lon ~t~blllty but
~l~o h-vlng good llght ~t-blllty. Th- compound- of
th- prc~cnt lnvcntlon ~upply thl~ nccd. Th-y form
ct~bl- di~p-r~lon~ ln c-rrl-t llquld-; th- lm~g~
d-v-lopcd ~lth thcm r- of ~ub~t-ntl-lly neutral
d-n~lty; nd th-~- compound~ o h-v- good llght
~t-billty.
Th- compound~ of th- lnventlon ~rc of
thc formul-
,o~
N . N
~o ~w 1'2
. N ~
bal
3~
`
~166631
wherein al iB low~r al~yl snd, R2 1- -F or
R3
-N ~
~ R4 , wherein R3 and R4 are hydrogen,
lower al~yl, phenyl, nspbthyl, or lower al~yl-
substituted phenyl or napbtbyl nd can be the ~ame
or different
Although the compound~ in which Rl i~
methyl and R2 i8 fluorine or amino ~re preferred,
the compound~ of the invention al~o include tho~e ln
which Rl ~nd R2 ~re other ~lmilar groups The~e
includo, in the case of Rl, other lower al~yls
such a8 thyl, n-propyl and t-butyl In ehe ca~e of
R they include mono- and disubstituted amino
groups ~uch ~ methylamino, dimethylamino,
methylethylamino, dl-t-butylsmino, diphenylamino,
d$tolylamino and nsphthylamino
The invention Jl~o includes an electro-
photographic liquid dev-loper comprising a dispet-
~ion of ~ pigment compound o~ defined above in an~l~ctric-lly in~ulat1ng c-rrier llquld
The compound~ of the inv-ntion can be
pr-p~r-d by the known method~ for pr-paring aromatic
t~-zo compound~ A pref-rred method i~ to form a
diazonium ~alt of an Jl~oxybenzene-~ulfonamite which
ha~ ao cetamido ~ub~tituent and then to couple two
mol-~ of the diazonium ~alt with one mole of
2,3-naphthalenediol Th- example~ which follow
illurtr-t- prepar-tion~ of interm-diate~ and of tho
de-ir-d fin-l compound~
ExamPle 1
~) Preparation of o-Acetanisidide
3S ~ ~ ~
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To 100 ~1 of c-tic nhydrlda w - add-d
dropwl~ with rtirring 100 g (0 813 mol~) of
o--ni-idin~, th~ t~mp~r~tur- ri-in8 to bout 60-C
during additlon. Tna r~actlon ~ixeura w-- h--tad on
S t~-m b-th for 15 minut~-, llow~d to cool to 45-C
and w-~ pourcd onto 500 g of cru-had ic-. The whlt-
~olld that pt-cipltatcd war coll-ct-d, wa~h~d fr--
of cid wlth w-tcr and ir dricd to giva 100 ~, m p
84-86-C, of product.
(b) Pr~p-r-tion of
3-~cetamido-4-methoxybenzene-ulfonamid~
~ ~ Cl ~ 3
lS ~ ~ ~ ~
o-~cat-nl-ldidc (100 g, 0 605 ~ol~) wa-
dd-d in portlon- to 200 1 of chloro~ulfonic cid
t bout 50-C ~coollng i~ n-c-~--ry). ~ft-r th~
ddltlon, th- ~olutlon w-~ h--tcd t 50-60-C for
four hourr, cool-d to roo~ tc~p~r-tur- and c-r~fully
dd-d to n lc--w-t-r mixtur- ~l.S ~g). Th- whit-
pr-clplt-t- w-~ coll-ct-d, w-~h-d with n ddltion-l
ount of w t-r ~1 llt-r) nd pr-rr-d dry with a
2S rubb r d~ for ~-v-r-l hourr. Th- d-mp ~ulfonyl
cblorld- w-r dlr~olv-d ln S00 ~1 of t-trahydrofuran,
cool-d to O-C nd tr--t-d wlth ~tr--m of ~mmoni-
g-c ~th- t-~p-r-tur- rl~lng xoth~r ic-lly to bout
2S-C) for 10 ~lnut~. Th- whlt- cryrt-llln- rolid
th-t r-p-r-t-d w-- coll-ct-d, w-rh-d wltb
100 1 of w-t-r nd drl-d to glv- 114 g ~80~ p.
227-230-C, of rulfon-~idc.
SS
~6631- -
~ c) PreParation of
1,4-Bi~(2-methoxy-5-sulfamoylphenylazo)-2,3-naphtb--
lenediol
~ 8Cl ~ ~ ;
N~202~BCOC ~ ~NO~ rl4
CJ~30
~ ,
~ ~
~ .
3-~cetamido-4-methoxybenzenesulfonamide
(72 4 g, 0 297 mol-) w-~ ~u~pent-t in 180 ml of 6N
hydrochloric acid and heat-d on a ~t-~m bath for 60
minut-~ Th- mber ~olution wa~ cool-t to 0C, the
r-~ultlng ~lurry w-~ treat-d with ~olution of 21 g
~0 30 mol~) of ~odium nltrite in 40 ml of wat~r
2S ~ft-r th- addition, the rolution wa~ ~tirred for 15
minut-z t O-C nd th-n filtered to remove any in~ol-
ubl- m-t-ri-l Th~ di-zonlum ~alt zolution wa~ th~n
ddod dropwi~c at 0-lO-C to ~tirrcd ~olution of
22 0 8 (0 142 ~ole) of 2,3-naphth-len-tiol in 900 ml
of pyridin-. Th- mixtur- waz ~tirred for one hour
t 0-5-C ~ft-r ddition w-- compl-t-, then ov~rnight
wlthout further cooling Th- dark ~olid wa~
coll-cted, wa-h-d with 100 ml of pyridin-, th-n
500 ml of meth-nol and fln-lly w-rm w-t-r to give
71.8 g of crud- product, ~ p Jbout 34S-C ~shrln~
ft-r drying Thl~ product wa~ ~lurried ia 500 ml
116663~
of refluxlng dimethylform-mld~ ~olv~nt for 30
minut~-. Th~ d~r~ mixture w-- cool~d to roo~
temp~rature, th~ ~olld w~a eollected, w--h~d wlth
methanol until tb~ filtrat- w-- eolorle~- nd dri~d
to giv- 62 8g (76S) of produet m p ~400-C.
Ex-mPle 2
(~) PreD-ration of
3-~c~tamldo-4-methoxvb~nzen~ulfon~l fluoride
To ~olution of 33 8 (0.35 mol~) of
10 pota~iu~ fluorid~ 2H20 in 500 ml of diox-ne/H20
(1 1) w-~ ~dd~d ~ equimol-r mount of
3-ac-tumldo-4-methoxybenz~n~ulfonyl chloride
prap-red a in Ex-mpl- l(b). Th~ r~action mixture
wa~ refluxed for 90 minut-~, th~n chill-d in an
ic~-b~th Th~ r~ulting whit- ~olid w~ collected
nd w--h~d wlth w-ter to giv~ 61 8 (72 5~) of th-
d--ir-d fluorid- m p 162-164-C.
(b)PraP-r-tion o
1,4-Bi~(2-methoxy-S-fluoro~ulfonylphenylazo)2,3-naph-
20 th~l-n-diol
Thi~ eompound w-- prep-r-d in the manner
d-aerib-d ln ExJmpl- l(e), but ub-tituting 8 9 g
(0.036 mol-) 3--e-t-~ido-4-m-thoxyb-nz-n-~ulfooyl
fluorid- for th- e-t-mido~ulfon-mid- of l~b) and
2S u~ing eotr-~ponding mount- of th- oth-r m-t-ri-l-
~ft-r w ~hing nd dtying th- mount of th- de~ir-d
eompound ~-~ 4.3 ~ ~35S), d-eompo~ing t 330 C
wlthout -ltln8
Th- leetrie-llg in~ul-ting e-rrl-r liquid
30 for th- d-v-lop-t eompoaltion~ of th- inv-ntion i- -
llquld of typ- ~oown in th- rt. ~ nown,
e-ttl-t llquld- fot l-ettophotogr-phle d~v-lop-ra
ebould h-v- lo~ dl-l-ettie eon~t-nt and v-r~
hlgh l-etrie-l r-~i-t-ne-. Suit-bl- llquid~ h-v- -
3S dl-l-etrie eon~t-nt 1--~ th-n 3 ~nd volum~
re~i~tlvit~ gre-ter th-n bout 101 ohm-em.
1166631
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They should also be st~ble under conditions of u~e.
Examples of carrler liqulds lnclude hydrocarbon
liqulds such a~ the lsopsraffinlc hydrocarbon~
having a boiling range from 145 to 185C whlch are
sold under the trademark "Isopar G." Others lnclude
halogenated hydrocarbon llquids boillng from 2C to
55C, for example, fluorinated hydrocarbon6, such as
trlchloromonofluoromethane and trichlorotri-
fluoroethane. Still other useful carrLer liquid~
include polysiloxane~, odorless mineral spirits,
octane and cyclohexane.
Although the developer can consl~t ~imply
of a dlspersion of a novel pigment of the invention
in the carrier llquid, it i~ u~ually des$rable to
include a binder polymer to fix the pigment
psrticles to the paper or film or other ~urface to
be developed. Especially u~eful a8 binder polymer~
are the acryllc copoly~er~ disclo~ed in Stahly et al
U.S. 3,849,165 and the polyesterionomers disclosed
in Merrill et al U.S. 4,202,785.
The liquld developer of the invention can
also contain a charge control agent to provlde
un$form charge polarlty on the developer particles
and to aid in stabilizing the disper~lon of pigment
and binder resin. The chsrge control agent is also
referred to as a stabilizer. The amount of charge
control ~gent i~ preferably in the range from 0.1 to
2 weight percent of the developer composition.
Examples of uoeful charge control agents or
stabilizers are disclosed in Stahly et al, U.S.
3,849,165, Ford et al, U.S. 4,145,299, Merrill
t 1, U.S. 4,170,563 and Merrlll et al, U.S.
4,229,513. Preferred polymeric charge control
gents ~nclude poly(styrene-co-lauryl
methacrylate-co-sulfo~thyl methacrylate),
1 16663
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poly(vlnyltolu ne-co-l-uryl -thacrylate-co-lithiu~
~eth-crylate-co--eth-crylic cld), poly(p-tert-butyl
tyrene-co-llthiu~ ~eth cryl-te) nd poly(vlnyl-
tolueno-co-lauryl ~ethacryl-te-co-~ thacryloyloxy-
ethyltrim thyl-~ oniu~-p-tolu ne ulfon-t-) They
are either ~olubl- or re-dily di~per~ible in the
usual hydroc-rbon carrier liquid- nd do not settle
out Non-poly~eric charge control agent- re ~180
useful such ~ the oap- of 4gnesium aod heavler
~etals disclo~ed ln the patent to Beyer, U S
3,417,019
The developer can bo prepared ~8 described
in Ford et 1 U S 4,145,299 by 8rindini or ball
~illing the pig -nt with a ~olutlon of the blnder
poly~er ln n ro~atlc hydrocarbon llquid to obtaln
a dev loper concentr-t- Thls 1- then dlluted wlth
th- ln-ul-tlng c-rrler llquid, uch 8 sn
i~opar-ffinlc hydrocarbon llquld, to obt-ln a
di~per~ion of th- pig~ nt nd binder poly~or The
charg- ag-nt, lf u~ed, c-n b- incorporat-d at the
a-~- ti~- or l-ter The dovelopor will contaln from
0 01 to 1 0 8r-~ of pig~-nt p-r liter of developer
Wh n bind-r poly r i~ u~-d th plgment to bind-r
welght r-tio c-n v-ry, 8 , fro- 1 20 to 2 1
2S Th following x-~pl- illu~trate~ the
pr-p-r-tioo of d-velop-r of the inventioo
X--Pl- 3
To 22 5 g of a 7 w lght p-rcent solution of
th ~t-billz~r poly~or, poly(vinyltolu-n--co-lauryl
-th eryl-t--eo-lithiu -th-cryl-te-co-~eth crylic
eit), ln "Solv ~o 100" ro~-tlc hydroearbon
~olv nt w-~ dd-d 2 8 Of th- plg~ont of Exa~pl- 1
("801v --o 100" i~ th- tr-do--rk for n lkyl-ted
ro-~tle hydroe-rbon ~ixtur- boillng fro 150 to
18SC) Th xixtur w ~ b-ll--ill-d for 15 d-ys to
.. . .
6663
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obtaln a disperslon conc-ntrat- To th~
concentr-te w-s added 9 3 g of 14 w ight p-rc-nt
solut~on of blnder polymer in "Solvesso 100"
- aromatic hydrocarbon The blnder poly~er w~s
S poly(ethyl acrylate-co-ethyl ethacrylate-co-l-uryl
methacrylato-co-lithlu~ sulfoethyl ~ethacryl-te)
quantlty of the ~ixture (4 2 8) was then dlsper~ed
in 500 ~1 of "I-opar G" isoparafflnlc carrler llquld
by ultrasonic ~eano
Example 4
In ~ub~tantlally the ~a~e manner a8 ln
Exs~ple 3 another developer of the inventlon was
prepared but u~ing dlfferent plg~ent, nsmely, the
pig~ent of Example 2
Thr-- other developers were prep~red ~ ln
Example 3 but u~lng instead of a pigment of the
lnventlon one of the followlng pigments
Control Exa~Dle S
~ N ~ 3
~-3
Control EXa~P1e 6
~1~
1 Y
OC~3
~-03 T~
OC~3
11~6631
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Control Exumple 7
~N
~ OC~3
N~N
In esch of the e~umples of the invention,
Ex~mples 3 and 4, and ~n the Control Examples 5-7
the p~gment~ formed stable d-veloper dispersions
Each developer wa8 usod to develop charge patterns
formed by unlformly charglng a polyethylene
terephthalate film In each instsnce the electro-
statlcally charged film surface wss ~ucc-ssfully
doveloped to substantlally black or noutral
density Each devoloped fll~ sample was then
sub~octqd to a llght f-dlng test The tost
con-l~ted of xpo~ur- to hlgh lntensity, simulated
north rn okyllght ov r a poriod of day~ The
re~ult~ of th- t-~t~ r- roport-d ln terms of Nigh
Intonolty D-yllght, whlch 18 a ot-ndard ~easure of
llght ~t-bllity t-~ting of lmages This is
abbr-viat-d ~ HID nd 1~ qual to 50,000 lux Thus
an HID xposure for perlod of one week (168 hours)
18 qual to 8 4 x 106 lux-hours ~ssu~ing that
th lnten~ity of av~rage northern skyllght is 2500
lux, lt c-n bc c-lculat-d that on- woek of HID
xposur- 18 equlv lont to 3,360 hour~ of northern
daylight xposur- ~8 4 x 106 lux-hour~/2500 lux
~ 3,360 hours) ~t 12 hour~ of dayllght per day,
280 d-y~ of ver-go northern dayllght Jre oquivalont
to on w-ek of HID expooure In tdltion to theoe
a~umptlono, certain othor assu~ptlons re relovant
1 166631
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to the re6ults li6ted below for the light stability
tests. The other assumption6 are ~hat there i8 no
photographic reciprocity effect, ~here i8 no inter-
mittency, the p~gments tested have equivalent
spectral energy distributions and in the test~ there
was no significant sensitivity to temperature or
humidity changes.
The test results were as follows:
Pi&ment Percent Fading
10Example 1 (Invention) 7 at 7 days HID
" 2 " 6.5 at 7 " "
3 (Control) 31 at 4
" 4 " 40 at 4 " "
~ 5 " 46 At 4
The test re6ults show that although all
five pigments formed satisfactory dispersions and
neutral density images, the pigments of the inven-
tion tExamples 1 and 2) were markedly superior to
the pigments of the control examples ln llght
20 stability or, in other words, in resistance to
fading when exposed to simulated northern 6kylight.
In addition to the uses described above,
the compounds of the invention can be components of
composite electrically photosensitive particles of
25 the type disclosed ln Merrill et al, U.S. Patent
No. 4,322,487 for use in photoelectrophoretic
migration imaging processes.
Although the invention has been described
in considerable detail with particular reference to
30 certain preferred embodiments thereof, variations
and modiflcations can be effected within the spirit
and scope of the invention.
r~
